Solubilized orange dye (dialkylsulfonamide derivative)

ABSTRACT

Novel dyes for plastic substrates which act as filters in such substrates for argon and double-frequency neodymium laser beams are sulfonamide derivatives of 12-H-naphthoperinone. These dyes are soluble in and compatible with the plastic substrate and provide stability to ultraviolet light.

United States Patent [191 Tucker et al.

[451 Sept. 30, 1975 SOLUBILIZED ORANGE DYE (DIALKYLSULFONAMIDEDERIVATIVE) Inventors: Robert Jerome Tucker,

l-lackettstown; Richard Specter, Kendall Park, both of NJ.

Assignee: American Cyanamid Company,

Stamford, Conn.

Filed: Jan. 7, 1974 Appl. N0.: 431,199

US. Cl 252/300; 260/4221; 260/2565 R Int. Cl. C08K 5/34; F21V 9/00 Fieldof Search... 252/300; 260/4221, 256.5 R

References Cited UNITED STATES PATENTS 1 H1970 Christmann et a1.260/4221 Primary Examiner-James H. Derrington Attorney, Agent, orFirm-William J. van Loo; John L. Sullivan 5 7 ABSTRACT 2 Claims, NoDrawings SOLUBILIZED ORANGE DYE (DIALKYLSULFONAMIDE DERIVATIVE) Thisinvention relates to novel compositions of matter. More particularly theinvention relates to dialkylsulfonamide derivatives ofl2-H-phthaloperinone, which derivatives are useful orange colorants forplastic materials.

In the preparation of various types of plastic optical filter orscreening materials, dyes with certain spectral characteristics areoften required so that the required spectral or light absorbingproperties may be obtained in the particular filters or screens beingprepared. To be useful in such applications, the dyes must be soluble inand compatible with the plastic substrate so that the dye does notmigrate to the surface of the plastic and exhibit blooming, orcrystallization. In addition, the dye must also possess stability tolight so as to provide a useful service life for the plastic filter orscreen. I

In accordance with the present invention, there is provided an orange oryellow colored dye of the general formula P g (so na wherein R is analkyl of l to 5 carbon atoms and n is an integer of l to 4.

The dyes of the present invention are improved in solubility,compatibility, and stability in plastic substrates, particularly inpolyvinyl chloride, over prior art materials.

In preparing the novel compositions of the present invention, thestarting material is conveniently 12-H- phthaloperinone, which iscommerically available as Aminoplast Orange LFP.

Reaction is carried out to introduce N,N-dialkylsulfonamide radicals onthe l2-H-phthaloperinone moiety in accordance with conventionalprocedures for such radicals on other moieties. Generally the reactionis carried out by treating the intermediate with chlorosulfonic acidunder conditions which preferably introduce two sulfonyl chlorideradicals on the 12H- phthaloperinone moiety and then subsequent reactionwith a dialkyl amine is carried out to provide theN,N-dialkyl-sulfonamide radicals.

Substitution of the l2-l-l-phthaloperinone will occur at the variousreactive sites of the phenyl and naphthyl ring portions of itsstructure. Actual positions substituted will vary depending uponreaction conditions employed and the amounts of reagents used ineffecting substitution. Under the usual conditions employed in preparingthe compound wherein n is 2, substitution on the naphthyl ring portionof the molecule predominates. It can be appreciated that on astatistical basis, a wide variety of positions can be occupied by theN.N-dialkylsulfonamide groups introduced and, therefore, the inventionis not limited to any specific positions occupied by theN,N-dia.lkylsulfonamide groups. Thus, it is possible that the productobtained in any given sulfonamidation reaction will be mixed withrespect to the positions occupied by the sulfonamide groups and withrespect to the specific number of substituents present on a givenmolecule. However, an average number of substituents and a predominatingsubstituent arrangement will prevail in most cases. The effectiveness ofthe compounds does not appear to be influenced by the particular speciesinvolved.

l2-l-l-phthaloperinone is the required starting material and noequivalents are known. This intermediate is chlorosulfonated inaccordance with conventional procedures, such as those described in U.S.Pat. Nos. 2,897,207 and 3,536,502 wherein sulfonamidation ofphthalocyanine derivatives is disclosed.

After chlorosulfonation is effected, amidation is carried out using asuitable dialkylamine. Suitable dialkylamine are those containing alkylgroups of l to 5 carbon atoms. Typical amines are dimethylamine,diethylamine, the dipropylamines, the dibutylamines, and thediamylamines. The amount of dialkylamine used is generally sufficient toeffect complete amidation of the chlorosulfonate groups introduced. Thenumber of chlorosulfonate groups introduced will generally vary from 1to 4 per mole of l2-H-phthaloperinone, with 2 being preferred.Conditions of reaction are sufficient to introduce the desired number ofsubstituents and excesses of sulfonyl chloride and amine may beemployed.

The. dyes of the present invention are especially use ful for coloringplastics, especially polyvinyl chloride, and because of their spectralcharacteristics, are useful in plastic compositions applicable asprotective filters against argon and double-frequency neodymium laserbeams; The dyes are used at effective levels in such uses and will dyethe plastic yellow to orange shades, depending upon the effective levelemployed. Typically, a usage level in the range of about 0.1 to 2.0%,based on the weight of plastic: may be used but other usage levels maybe employed so long as effective filtering is obtained. In addition topolyvinyl chloride, one may use such plastics as polyvinylidenechloride, polyvinyl bromide, polyvinylidene bromide,polytrifluoroethylene, polytetrafluoroethylene, polyacrylonitrile,polystyrene, polymethyl methacrylate, and the like.

The invention is more fully illustrated by the examples which follow.

EXAMPLE 1 PREPARATION OF BlS(N,N-DIBUTYLSULFONAMIDO)- l2-HPHTHALOPERlNONE To 195 grams of chlorosullfonic acid were addedgradually with stirring 32.4 grams of l2-H- phthaloperinone. The mixturewas heated to C. over a period of 2 hours after which it was cooled toroom temperature. Then 30 milliliters of thionyl chloride as addeddropwise and the solution was heated at 80C. for 2 hours.

After standing overnight, the reaction mixture was drowned in 900milliliters of ice-water with 132 grams sodium chloride added,maintaining the temperature at C. by addition of ice as necessary. Thedisulfonyl chloride substituted intermediate which precipitated wasisolated by filtration and washed with ice-water.

The solid intermediate was then reacted with butylamine. The orangeintermediate was suspended in a mixture of 900 ml. of water and 600 g.ice. To the mixture, 210 ml. di-n-butylamine was added, followed by 60g. sodium bicarbonate and 300 ml. acetone. After stirring vigorously forone hour the gummy solid which had formed was isolated by filtration andthen dissolved in anhydrous ethanol. To the solution was added 3 litersof water containing 100 grams of sodium chloride and 50 ml. concentratedhydrochloric acid. After stirring further, the gummy residue was removedand dissolved in anhydrous ethanol and clarified. An orange solidprecipitated, was removed and recrystallized once from anhydrous ethanolto yield the product bis(N,N- dibutylsulfonamido)-12-H-phthaloperinone.

EXAMPLE 2 POLYVINYL CHLORIDE COMPOSITION A (nm). 0.0

Wavelength of argon ion laser Wavelength of argon ion laser Wavelengthof double ncndymiun laser After 500 hours Fadeometer exposure, the chipwas in excellent condition and the optical density values had notchanged. After 7 months, the chip still exhibited no signs ofincompatibility of contents.

COMPARATIVE EXAMPLE A Following the procedure of Example 2, a similarchip was prepared employing in place of the dye of Example 1, an equalamount of 12-I-I-phthaloperinone.

Upon exposure of the chip to ultraviolet light in the Fade-ometer for 3hours, the dye exhibited blooming and exuding from the plastic,illustrating a high level of incompatibility.

EXAMPLE 3 POLYVINYL CHLORIDE COMPOSITION The procedure of Example 2 wasfollowed in every material detail except that 0.6 gram of the dye of Example l was employed instead of 0.265 gram and the chip thickness was 54mm. Examination of the chip gave the following results:

EXAMPLES 4-1 1 Following the procedure of Example 1 a series ofN,N-dialkylsulfonamide derivatives of 12-H- phthaloperinone areprepared. The various derivatives are listed below.

EXAMPLE ALKYL methyl ethyl ethyl n-propyl iso propyl umyl amyl methylEXAMPLE 12 Following the procedure of Example 2 each of the compounds ofExamples 41 1 are evaluated in polyvinyl chloride chips. In eachinstance substantially the same results as exhibited by the dye ofExample 1 are obtained.

We claim:

1. A composition of matter comprising a plastic material selected fromthe group consisting of polyvinyl chloride, polyvinylidene chloride,polyvinyl bromide, polyvinylidene bromide, polytrifluoroethylene,polytetrafluoroethylene, polyacrylonitrile, polystyrene and polymethylmethacrylate having incorporated therein an effective, light-filteringamount of dye compound of the formula:

wherein R is an alkyl group offrom 1 to 5 carbon atoms and n is aninteger of from 1 to 4.

2. A composition according to claim 1 wherein the plastic material ispolyvinyl chloride and the dye compound has the formula:

1. A COMPOSITION OF MATTER COMPRISING A PLASTIC MATERISL SELECTED FROMTHE GROUP CONSISTING OF POLYVINYL CHLORIDE, POLYVINYLIDENE CHLORIDE,POLYVINYL BROMIDE, POLYVINYLIDENE BROMIDE, POLYTRIFLUOROETHYLENE,POLYTERTRAFLUOROETHYLENE, POLYACRYLONITRILE, POLYSTRYRENE AND POLYMETHYLMETHACRYLATE HAVING INCORPORATED THEREIN AN EFFECTIVE, LIGHT-FILTERINGAMOUNT OF DYE COMPOUND OF THE FORMULA:
 2. A composition according toclaim 1 wherein the plastic material is polyvinyl chloride and the dyecompound has the formula: